Tack composition for elastomeric polymers



United States Patent 3,545,991 TACK COMPOSITION FOR ELASTOMERIC POLYMERSRalph W. Body, Wilmington, Del., assignor to Hercules Incorporated,Wilmington, Del., a corporation of Delaware No Drawing. Filed May 1,1967, Ser. No. 634,847 Int. Cl. C08h 11/04 US. Cl. 106-239 10 ClaimsABSTRACT OF THE DISCLOSURE A composition of matter comprised of (A) astabilized rosin such as hydrogenated rosin, (B) rosin amine, and (C) anoil such as a naphthenic oil is used to provide a tacky surface onelastomeric polymers such as EPR and EPDM. The tacky surface providesadequate building tack for the manufacture of automobile tires and thelike.

This invention relates to the synthetic rubber art.

Particularly, this invention relates to a novel composition of matteradapted particularly for application, preferably in the form of asolution thereof in a solvent, to the surface of rubbery copolymers ofethylene and another copolymerizable monomer selected fromot-monoolefins such as propylene (rubbery copolymers of ethylene andpropylene being sometimes referred to in the art as EPR) and to thesurface of vulcanizable unsaturated rubber-like interpolymers ofethylene, at least one other copolymerizable monomer selected fromu-monoolefins, and at least one nonconjugated hydrocarbon diene, toprovide thereon, after solvent removal, a tacky surface.

In the preparation of articles from synthetic rubber, it is oftennecessary to assemble articles from smaller pieces. For example, a tireis usually constructed or built by applying layers of rubber-coatedfabric one to another, followed by a breaker strip, cushion, and tread.The layers must possess sufficient surface tack to adhere firmly one toanother and to maintain the desired relative position of the variousparts prior to vulcanization. Absence of tack in many cases causesdifficulty in the building operation. Thus, tack is an importantproperty in the tire-building field for here it is necessary to put thevarious parts of the tire together in a matter of minutes such as, forexample, about 2 minutes to 5 minutes, in order that the operation beeconomically feasible. Since tires generally comprise from 2 to plies,it is apparent that the surface of the plies must adhere readily one toanother in order to permit rapid building and yet produce a tire thatwill not prove faulty in use. Tack is also important in all applicationsrequiring the laying-up of piles such, for example, as in hosemanufacture and in belt manufacture.

Recently, there has been introduced to the tire manufacturer a sulfurvulcanizable unsaturated rubberlike (elastomeric) interpolymer of (1)ethylene, (2) at least one a-olefin, such as propylene, having thestructure I.-CH=CH Where R is a C -C alkyl radical, and (3) anonconjugated hydrocarbon diene such, for example, as 1,4-hexadiene anddicyclopentadiene. To date, the most interesting commercially of theelastomeric polymers are those derived from ethylene, propylene, and anonconjugated hydrocarbon diene. An elastomeric interpolymer of thistype is referred to in the art as an unsaturated, vulcanizable, rubberyterpolymer of ethylene, propylene, and a copolymerizable diene;ethylene-propylene terpolymer (EFT) and ethylene-propylene-dienemethylene (EPDM).

These elastomeric interpolymers do not have sufficient tack to be usedeconomically in the manufacture of tires for automobiles, and the like.This is a fact well known in 3,545,991 Patented Dec. 8, 1970 the art andmany attempts have been made to solve this problem. The ditficulty,industry-wide, is to develop tack Without impairing the vulcanizationrates and without impairing the properties of vulcanizates such asmodulus, elongation, heat build-up, and the like.

In accordance with this invention there is provided a novel compositionof matter adapted for application to the surface of an elastomericpolymer member that lacks surface tack, such as EPR and EPDM, to providesaid member with a tacky surface.

The novel composition of this invention is comprised of (A) asubstantially stable modified rosin such as hydrogenated rosin anddisproportionated rosin; (B) rosin amine; and (C) an extender oil forrubber selected from the group consisting of naphthenic oil, aromaticoil, highly aromatic oil and mixtures thereof. The range of proportionsof the components (A), (B) and (C) can be varied to a substantialdegree; however, the preferred range for the purpose of this inventionis, by weight, from about 5 parts to 10 parts of rosin component (A),from about 1 part to 5 parts of rosin amine component (B), and fromabout 1 part to 10 parts of oil component (C).

Application of the above composition to a surface of an elastomericpolymer member, such as EPR and EPDM, is made preferably from solution.Suitable solvents for the composition will be a solvent or a mixture ofsolvents that will dissolve substantially all three components of thecomposition, is inert to the components of the composition and is alsoinert to the elastomeric polymer member to which the solution isapplied. Suitable solutions will be comprised of, by weight, from about5% to about 50% of solids, and preferably from about 10% to about 20solids. Too low a solids content requires two or more applications andtoo high a solids concentration is difficult to apply conveniently.

Suitable solvents for use herein include aromatic hydrocarbons such asbenzene, toluene, and the like; ketones such as acetone, methyl ethylketone, methyl isobutyl ketone, and the like; aliphatic hydrocarbonssuch as hexane, heptane, octane, gasoline, and the like; and chlorinatedhydrocarbons such as methylene chloride, chloroform, carbontetrachloride, and the like. Mixtures of two or more solvents can beused if desired.

Rosin component (A) is a rosin, such as Wood rosin, gum rosin, or talloil rosin, that has been modified by means of hydrogenation, by means ofthe disproportionation reaction, or the like, whereby the rosin iseffectively modified to render it substantially less susceptible to airoxidation. Rosin, as used herein, means natural rosin, refined orunrefined, such as natural wood rosin, natural gum rosin, and tall oilrosin; the pure rosin acids of which rosin is comprised such as abieticacid and d-pimaric acid, alone or in admixture with one another; andmixtures of any two or more of the above.

Hydrogenated rosin, which can be used as rosin component (A), is wellknown in the art and is derived by hydrogenating rosin as such whichconsists mainly of abietic acid, pimaric acid, and the like rosin acidsunder conditions suitable to achieve saturation of at least about 50% ofthe available two double bonds of the rosin acid radicals present. Theterm hydrogenated rosin includes similarly hydrogenated products derivedfrom any of the groups of rosin acids in substantially pure form ormixtures of the pure rosin acids. Hydrogenated rosin can be prepared,for example, by contacting fluid, refined rosin with hydrogen in thepresence of an activated nickel catalyst under a pressure of about 4000to 5000 pounds per square inch and at a temperature of about 210 C. toabout 230 C. Suitable methods for producing hydrogenated rosin aredescribed in Pat. 2,094,117, reference to which is hereby made.

Disproportionated rosin, which can be used as component (A), can beprepared from any suitable rosin material including gum rosin, woodrosin, and tall oil rosin and in any suitable manner as by heattreatment in the presence of a catalyst such as iodine, sulfur dioxide,platinum and the like known catalyst. Suitable methods for effectingdisproportionation of rosin are disclosed in Pat. 2,138,183, referenceto which is hereby made. Commercially available disproportionated rosinswill contain usually, by weight, about 0.5% abietic acid, from about 40%to 60% dehydroabietic acid, and the remainder mostly dihydro rosin acidsand a small amount of neutral materials. Mixtures of disproportionatedrosin and hydrogenated rosin can be used if desired.

The monomeric rosin acid distillate obtained as a byproduct of rosinpolymerization is a stabilized rosin that can be used as rosin component(A). It has good resistance to air oxidation and has good stability toheat and light. This monomeric rosin acid distillate will usuallycontain, by weight, about 89% resin acids, and about 11% neutralmaterial. Of the resin acids about 76% are the stabilized type such asdehydroabietic acid, dihydroabietic acid, and tetrahydroabietic acid.

Rosin amine component (B) is an unsubstituted rosin amine and can beprepared from wood rosin, gum rosin, tall oil rosin and mixtures thereofby the method disclosed and described in Pat. 2,491,913, reference towhich is hereby made. Briefly, the rosin acid component of rosin isfirst converted to a corresponding nitrile. Reaction is carried out bypassing gaseous ammonia into fused rosin and vaporizing water as fast asit is formed to remove water from the reaction mass. Subsequently, thenitriles are preferably purified by neutralization and distillation. Thenitriles are then subjected to hydrogenation to produce thecorresponding amine. Any active hydrogenation catalyst such, forexample, as nickel cobalt, Raney nickel, Raney cobalt and the like canbe used in the hydrogenation reaction.

A suitable rosin amine that can be used in this invention is comprisedof by weight about 70% dehydroabietylamine and about 30%dihydroabietylamine and tetrahydroabietylamine. Dehydroabietylamine canbe represented by the structural formula HaC G HzNHI HaC The oilcomponent (C) can be any of those oils that have been used heretofore inthe rubber art as extending oils. A wide range of oils having variouschemical and physical properties are thus included. Any of the wellknownoils that are compatible with rubber, ranging from very light to veryviscous, can be used as component (C). Suitable oils include those knownin the rubber art as naphthenic oils, aromatic oils, and highly aromaticoils. Mixtures of two or more can be used if desired. Preferred oils areof the naphthenic type.

A particularly suitable naphthenic oil for use in this invention is thatavailable commercially under the proprietary designation Circosol 2XHwhich is a light lubricating oil fully described in Rubber Age, vol. 70,No. 6, pages 735-747, March 1953, and a product of Sun Oil Company. Thisoil contains naphthenic hydrocarbons of high molecular weight in theform of a heavy, viscous, transparent, ale green, odorless liquid of lowvolatility;

it has a specific gravity at 25 C. of 0.940 and a viscosity of about2000 SUS at 100 F.

Another suitable naphthenic oil is that available under the proprietarydesignation Circosol 2X which is a naphthenic-type hydrocarbon oilcontaining some aromatic oil. It is a light green viscous hydrocarbonliquid having a specific gravity of 0.94, a viscosity of 200 SUS at 100F. and a viscosity of SUS at 210 F.

The sulfur-vulcanizable elastomeric interpolymers to which thisinvention is applicable are derived by copolymerizing ethylene; ana-monoolefin having the structure R-CH=CH wherein R is an alkyl radicalof not more than 8 carbon atoms; and a nonconjugated hydrocarbon diene,by known methods.

Examples of useful ot-monoolefins having the structure RCH=CH as abovedefined, include propylene; l-butene; l-heptene; l-decene; l-pentene;S-methyl-lhexene; 4-methyl-1-pentene; l-octene; 5,5-dimethyl-loctene;4-methyl-l-hexene; 4,4-dimethyl-l-pentene; 1- hexene; l-nonene;S-methyl-l-nonene; S-methyl-l-heptene; 6-methyl-1-heptene;4,4-dimethyl-l-hexene; and 5,6,6-trimethyl-l-heptene.

Examples of dienes include dicyclopentadiene; tricyclopentadiene;tetracyclopentadiene; 5 alkenyl substituted 2 norbornene; 5 methylene2-norbornene; and 2-alkyl- 2,5-norbornadienes.

Another suitable diene is an aliphatic diene having the structure Ra RaCHz=CHR1-C=CR4 wherein R is an alkylene radical; R and R are selectedindependently from the group consisting of hydrogen and alkyl radicals;and R is an alkyl radical; and wherein R through R, are so selected thatthe aliphatic diene has from about 6-22 carbon atoms. Specific examplesof aliphatic dienes having the above structure (I) include 1,4-hexadiene; 1,9 octadecadiene; 6 methyl 1,5-heptadiene; 7 methyl 1,6octadiene; 11-ethyl1,1l-tridecadiene; 9 ethyl 1,9 undecadiene; 7ethyl-1,7 nonadiene; 8- propyl 1,8 undecadiene; 8 ethyl-1,8-decadiene;10- ethyl 1,9 dodecadiene; 12 ethyl-1,12-tetradecadiene; 13 n butyl1,12-heptadecadiene; and 15-ethyl1,15- heptadecadiene. Dienes such as 11ethyl 1,11 tridecadiene are made by reacting an alkyl Grignard reagentwith the alkyl ester of an omega-unsaturated carboxylic acid anddehydrating the tertiary alcohol thereby produced.

Examples of interpolymers of ethylene, at least one a-monoolefin, and atleast one of the above aliphatic dienes include ethylene/ propylene/ 1,4hexadiene; ethylene/1 butene/ 1,4 hexadiene, ethylene/'1 butene/ 1,4-hexadiene/ 11 ethyl 1,11 tridecadiene; ethylene/1- butene/l octene/ 6methyl 1,5-heptadiene; and ethylene/ l-pentene/ 1,4,hexadiene/1,9-octadecadiene.

Examples of interpolymers of ethylene, at least one amonoolefin as abovedefined, and dicyclopentadiene include ethylene pro pylene/dicyclopentadiene;

ethylene/ 1-butene/dicyclopentadiene; ethylene/propylene/1-butene/dicyclopentadiene; ethylene/ 1-octene/dicyclopentadiene;ethylene/propylene/ 1-hexene/dicyclopentadiene; ethylene/ l-heptene/l-decene /dicyclopentadiene and ethylene /5-methyl-1-heptene/dicyclopentadiene.

The diene employed to prepare the polymers used in this invention can be5 alkylidene 2 norbornene, such as 5 methylene 2 norbornene and5-ethylidene-2- norbornene. 5 methylene 2 norbornene can be prepared bythe method disclosed and described in Pa 3, 6

620, reference to which is hereby made. S-methylene-Z- norbornene can berepresented by the structure Examples of interpolymers of ethylene, atleast one ozmonoolefin as defined above, and S-methylene-Z-norborneneinclude ethylene/propylene/ S-methylene-Z-norbornene;

ethylene/ 1-butene/5-methylene-2-norbornene;

ethylene/ 1-decene/S-methylene-Z-norbornene;

ethylene/ 5,5 -dimethyl-1-octene/ S-methylene-Z- norbornene;

ethyle ne/4-methyll-hexene/ 5 -methylene-2-n0rbornene;

ethylene/ 4,4-dimethyl-1-pentene/ 5 -methylene-2- norbornene; and

ethylene/ 5 6,6-trimethyll-heptene/ 5 methylene-2- norbornene TheS-alkenyl-Z-norbornenes that can be employed in preparing theinterpolymers used in this invention can be represented by the structure(III) wherein each X represents hydrogen or a monovalent alkyl radicalof from 1 to 6 carbon atoms and Z represents a monovalent alkenylradical, the carbOn-to-carbon double bond therein being internal.Specific examples of 5 alkenyl 2 norbornenes include 5-(2'-butenyl)-2-norbornene derived from cyclopent-adiene and 1,4-hexadiene; 5 (1'propenyl) 2 norbornene derived from cyclopentadiene and 1,3-pentadiene;

5- 2-ethy1-2'-butenyl) -2-norbornene; 5-(2'-ethyl-1 butenyl)-2-norbornene;

5- (2'-methyl-1-propenyl) -2-norbornene; 5- 2-propyl-2'-pentenyl)-2-norbornene;

5 2hexyl-2'-undecenyl) -2-norbornene; 5- (2'-nonyl-2'-heptenyl)-2-norbornene; 5-(2-butyl-1-pentenyl)-2-norbornene;

5- (2'-pentyl-1-octenyl) -2-norbornene;5-(2-heptyl-1-undecenyl)-2-norbornene; 5- 2'-rnethyl-2'-butenyl)-2-norbornene;

5- (2-methyl-2'-decenyl) -2-norbornene; 5-(2'-methyl-1-bu-tenyl-2-norbornene; 5-(2'-methyl-1'-hexenyl) -2-norbornene; 5-(2-methyl-1'-undecenyl) -2-norbornene; 5-( 2-heXyl-2'-butenyl-2-norbornene;

5- 2-octyl-2'-butenyl -2-norbornene 5- 2'-ethyl-2'-deeenyl-2-norbornene'; and 5-(2'-ethyl-1'-octenyl)-2-norborne.

Examples of interpolymers of ethylene, at least one umonoolefin, and a5-alkenyl-2-norbornene include ethylene/propylene/S- (2-butenyl)-2-norbornene;

ethylene/propylene/S- (2'-ethyl-2'-butenyl -2- norbornene;

ethylene /propylene/ 5 (2-ethyl- 1 -butenyl -2- norbornene;

ethylene/propylene/ 5-( l-propenyl) -2-norbornene;

ethylene/ 1 -butene/ 5- (2'-heptyll '-undecenyl) -2- norbornene;

ethylene/ 1-butene/5-(2'-butenyl) -2-norbornene;

ethylene/ l-butene/ 5- 2-ethyl-2-butenyl -2- norbornene;

. manufacture,

ethylene/4,4-dimethyll-hexene/ 5- (2'-propyl-2- pentenyl -2-norbornene;

ethylene/ 5 ,5 -dimethyl- 1 -octene/ 5 (2-nonyl-2'- heptenyl -2-norbornene;

ethylene/ 6-methyll-heptene/ 5 2'-methyl-2-decenyl 2-norbornene;

ethylene/ l-decene/S-(2-hexyl-2'-buteny1)-2- norbornene; and

ethylene/ 5 ,6,6-trimethyl-l -heptene/ 5- 2'-octyl-2'- butenyl-2-norbornene.

2-alkyl-2,S-norbornadienes can be employed as the diene component andcan be represented by the structure where R is a C -C alkyl radical.These dienes are made by heating acetylenes having the formula R-CECH,where R is a C -C alkyl radical, with cyclopentadiene at 175 C. to 225C. in the absence of a polymerization initiator. Closed reaction vesselsmade from stainless steel or glass-lined steel are satisfactory.

Interpolymers of ethylene, at least one a-monoolefin, as abovedescribed, and a 2-alkyl-substituted 2,5-norbornadiene include ethyleneprop ylene/ 2-methyl-2,5 -norbornadiene;ethylene/propy1ene/2-ethyl-2,5-norbornadiene; ethylene/ 1 -butene/2-methyl-2,S-norbornadiene; ethylene/1-hexene/2-ethyl-2,S-norbornadiene; ethylene/1-decene/2-buty1-2,5-norbornadiene; and ethylene/l-heptene/2-octy1-2,5-norbornadiene.

Sulfur-vulcanizable elastomeric interpolymers of ethylene, propylene,and 1,4-hexadiene containing from about 1-15 mole percent of1,4-hexadiene and not over 75 weight percent of ethylene, having aniodine number of from 3-50 and an intrinsic viscosity in benzene at 25C. from about 0.5-5.0, are particularly suitable for use in themanufacture of automobile tires, and the like. The interpolymer andrelated interpolymers, and their method of are disclosed and describedin Pat. 2,933,480, reference to which is hereby made.

Sulfur-vulcanizable elastomeric interpolymers that also have particularutility in the manufacture of tires and the like are the interpolymersconsisting of ethylene, propylene, and dicyclopentadiene having at leastabout 20% to about 74.5% of ethylene units and at least 2579.5% ofpropylene units by weight and about 05-10% of dicyclopentadiene units byweight in the interpolymer. Interpolymers of this type and relatedinterpolymers as well as their method of preparation are disclosed anddescribed in Pat. 3,000,866, reference to which is hereby made.

Interpolymers derived from S-alkenyl-Z-norbornenes and their method ofpreparation are disclosedv and described in Pat. 3,093,620, reference towhich is hereby made. These interpolymers can be defined assulfurvulcanizable elastomeric interpolymers of ethylene, at least oneu-olefin having the structure RCH:CH wherein R is a C -C alkyl radical,and 5-alkenyl-2-norbornene, the said alkenyl radical having from 3-18carbon atoms, the carbon-to-carbon double bond of the alkenyl radicalbeing internal. The interpolymers have an iodine number between about 5and 60 and contain at least about'20% ethylene units by weight, at least25% of u-olefin units by weight, and at least about 0.03 gram-mole pergrams of said copolymer and not over about 20% by weight of saidinterpolymer of S-alkenyl-Z-norbornene.

Interpolymers derived from S-methylene-Z-norbornene and their method ofpreparation are disclosed and described in Pat. 3,093,621, reference towhich is hereby made. These interpolymers can be defined assulfurvulcanizable elastomeric interpolymers of ethylene, at least onea-olefin having the structure RCH=CH wherein R is a C -C alkyl radical,such, for example, as propylene, and -methylene-2-norbornene. Theinterpolymers contain at least about of ethylene units by weight, atleast of a-olefin units by weight, and at least about 0.03 gram-mole per100 grams of the interpolymer and not over about 20% of the interpolymerof 5-methylene-2-norbornene.

Interpolymers derived from 2-alkyl-norbornadiene and their method ofmanufacture are disclosed and described in Canadian Pat. 699,044 of Dec.1, 1964, reference to which is hereby made. These interpolymers can bedefined as sulfur-vulcanizable elastomeric interpolymers of ethylene, atleast one a-monoolefin having the structure RCH:CH wherein R is an alkylradical of from 1-8 carbon atoms and at least one 2-alkyl-norbornadienehav- 8 EXAMPLE 2 Hydrogenated rosin, 5 parts, rosin amine, 5 parts, andnaphthenic oil (Circosol 2XH), 1 part, are dissolved in 100 parts oftoluene to provide a solution which is subsequently applied to a sheetof elastomeric material prepared in accordance with Example 1. Thetoluene solvent is subsequently removed by evaporation at roomtemperature. The surface of the elastomeric sheets becomes tacky afterabout /2 hour and remains tacky for about 3 days. The tacky surface thusprovided permits of tire building in a time substantially shorter thanthe 20 to minutes required heretofore. The applied composition has noadverse effects on cure properties.

Examples of other compositions of this invention are set forth in TableI. All compositions, when tested in accordance with Example 2, provide asurface coated elastomeric terpolymer sheet having good tire buildingtack.

TABLE I Hydro- Disproporgenated tionated Rosin Oil (Circosol rosin,rosin, parts amine, 2XH), parts parts parts Solvent Parts Example No.:

ing from about 8 to 24 carbon atoms. The interpolymers have an iodinenumber between 5 and 60 and contain from about 2072.5% by weight ofethylene units, 2577.5% by weight of a-monoolefin units, and not morethan about 25 of norbornadiene units.

Methods of preparing some of the above interpolymers and relatedterpolymers are also disclosed and described in Pats. 3,162,620 and3,211,709, reference to which is hereby made.

Interpolymers derived by using methyl tetrahydroindene as at least oneof the nonconjugated dienes are suitable for the purposes of thisinvention. Such interpolyrners and their method of preparation aredisclosed and described in Belgian Pat. 637,939, reference to which ishereby made. Methyl tetrahydroindene can be represented by thestructural formula lIaC I J The EPDM used in this example is a rubberterpolymer containing on a weight basis about ethylene, about propylene,and about 5% 1,4-hexadiene, and on a rubber basis, about 52% ethylene,about 46% propylene, and about 2% 1,4-hexadiene and has a Mooney ofabout ML-4212 F. The following components are thoroughly milled andsubsequently sheeted by conventional means.

Component: Parts EPDM as above described HAF Black (carbon black) 50Zinc oxide 5 Tetramethylthiuram monosulfide 1.5 Z-mercaptobenzthiazole0.75 Sulfur 1.5

Another tackifier composition for use as a surface cement or tackifierfor EPR, EPDM, and like elastomeric materials consists of a stabilizedrosin such as disproportionated rosin and triethanolamine in a solventsuch as those hereinabove described.

As above set forth, the novel compositions of this invention can be usedto provide surface tack for rubbery or elastomeric copolymers ofethylene and another copolymerizable monomer selected froma-monoolefins. An elastomeric copolymer of ethylene and propylene,referred to as EPR, is an example of the above copolymers. Specificexamples of suitable copolymers of ethylene and propylene are those thathave a propylene content of from about 25 mole percent to 60 molepercent and which have a reduced specific viscosity within the range ofabout 2 to about 8. See British Pat. 857,183 for a description of suchelastomeric copolymers.

Known extending oils for rubber can be incorporated into the elastomericcompositions of this invention. The extending oils which can be usedcover a wide range of oils having various chemical and physicalproperties. Any of the well-known oils that are compatible with rubber,ranging from very light to very viscous, can be used as extending oilsin accordance with well-known practices. Whitby (Synthetic Rubber, p.219, John Wiley & Sons, 1954) indicates that extender oils can bedivided into three broad classes, namely, naphthenic, aromatic, andhighly aromatic. For nondiscoloring rubbers, naphthenic oils are usuallyemployed, while aromatic and highly aromatic Oils are preferred fordiscoloring rubbers. Thus, suitable extender oils include pine tar,light lubricating oils, and the like. Circosol ZXH (a proprietarydesignation) is a light lubricating oil fully described in Rubber Age,vol. 70, No. 6, pages 735-747, March 1953, and is a proprietary productof Sun Oil Company, and is a particularly suitable extender oil.Circosol ZXH contains hydrocarbons of high molecular weight, in the formof a heavy, viscous, transparent, pale green, odorless liquid of lowvolatility; it has a specific gravity of 0.940, and a Saybolt Universalviscosity at 100 F. of about 2000 seconds. Other extender oils aredisclosed and described in 9 U8. Pat. 2,964,083, reference to which ishereby made. The amount of extender oil employed will be from about 15to 150 parts by weight for each 100 parts by Weight of rubber component.

The usual fillers, reinforcing agents, antioxidants, vulcanizers,extenders, plasticizers, softeners, processing aids, as well asactivators and accelerators well known in the preparation of naturalrubber and synthetic rubber compositions, can be employed in preparationof the elastomerie compositions.

Fillers that can be employed include aluminum flake, antimony sulfide,asbestos, barium sulfate, cadmium sulfide, appropriate grades of carbonblack, chromic oxide, clay, such as bentonite, cotton linters, ironoxide, lime, litharge, lithopone, magnesium carbonate, magnesium oxide,silica, slate flour, talc, titanium oxide, whiting, Zinc oxide, zincsulfide, and the like. Zinc oxide, reinforcing grades of carbon black,hydrated silica, calcium carbonate, and the like, can be employed asreinforcing agents. Suitable pigments, such as ultramarine, vermillion,or the like, can be employed to impart to the composition a desiredcolor.

It is to be understood that the above description and examples areillustrative of this invention and not in limitation thereof.

What I claim and desire to protect by Letters Patent 1s:

1. A composition of matter consisting essentially of, by weight,

(A) from about 5 parts to about parts of a modified rosin selected fromthe group consisting of disproportionated rosin, hydrogenated rosin, andmixtures thereof,

(B) from about 1 part to about 5 parts of an unsubstituted rosin amine,and

(C) from about 1 part to about 10 parts of naphthenic oil.

2. A composition of matter consisting essentially of,

by weight,

(A) from about 5 parts to about 10 parts of a modified rosin selectedfrom the group consisting of disproportionated rosin, hydrogenatedrosin, and mixtures thereof,

(B) from about 1 part to about 5 parts of an unsubstituted rosin amine,and

(C) from about 1 part to about 10 parts of aromatic oil.

3. A composition of matter consisting essentially of,

by weight,

(A) from about 5 parts to about 10 parts of a modified rosin selectedfrom the group consisting of disproportionated rosin, hydrogenatedrosin, and mixtures thereof,

(B) from about 1 part to about 5 parts of an unsubstituted rosin amine,and

(C) from about 1 part to about 10 parts of highly aromatic oil.

4. The composition of claim 1 wherein rosin component (A) isdisproportionated rosin.

5. The composition of claim 1 wherein rosin component (A) ishydrogenated rosin.

6. A composite member comprised of (1) a member comprised of anelastomeric polymer selected fromthe group consisting of (a) elastomericcopolymers of ethylene and at least one a-olefin having the structureRCH=CH wherein R is a C -C alkyl radical, (b) unsaturated interpolymersof ethylene, at least one a-olefin having the structure RCH=CH wherein Ris a C -C alkyl radical, and at least one nonconjugated hydrocarbondiene, and (c) mixtures of (a) and (b), and (2) a tacky coating on thesurface of said member, said coating being a composition of matterconsisting essentially of, by weight, from about 5 parts to about 10parts of a modified rosin selected from the group consisting ofdisproportionated rosin, hydrogenated rosin, and mixtures thereof, fromabout 1 part to about 5 parts of an unsubstituted rosin amine, and fromabout 1 part to about 10 parts of naphthenic oil.

7. A composite member comprised of (1) a member comprised of anelastomeric polymer selected from the group consisting of (a)elastomeric copolymers of ethylene and at least one a-olefin having thestructure wherein R is a C -C alkyl radical, (b) unsaturatedinterpolymers of ethylene, at least one a-olefin having the structureR-CH=CH wherein R is a C -C alkyl radical, and at least onenonconjugated hydrocarbon diene, and (c) mixtures of (a) and (b), and(2) a tacky coating on the surface of said member, said coating being acomposition of matter consisting essentially of, by weight, from about 5parts to about 10 parts of a modified rosin selected from the groupconsisting of disproportionated rosin, hydrogenated rosin, and mixturesthereof, from about 1 part to about 5 parts of an unsubstituted rosinamine, and from about 1 part to about 10 parts of aromatic oil.

8. A composite member comprised of (1) a member comprised of anelastomeric polymer selected from the group consisting of (a)elastomeric copolymers of ethylene and at least one a-olefin having thestructure wherein R is a C -C alkyl radical, (b) unsaturatedinterpolymers of ethylene, at least one u-olefin having the structureRCH=CH wherein R is a C -C alkyl radical, and at least one nonconjugatedhydrocarbon diene, and (c) mixtures of (a) and (b), and (2) a tackycoating on the surface of said member, said coating being a compositionof matter consisting essentially of, by weight, from about 5 parts toabout 10 parts of a modified rosin selected from the group consisting ofdisproportionated rosin, hydrogenated rosin, and mixtures thereof, fromabout 1 part to about 5 parts of an unsubstituted rosin amine, and fromabout 1 part to about 10 parts of highly aromatic oil.

9.'A composite member in accordance with claim 6 'wherein the rosincomponent of the composition of matter is disproportionated rosin.

10. A composite member in accordance with claim 6 wherein the rosincomponent of the composition of matter is hydrogenated rosin.

References Cited UNITED STATES PATENTS 2,491,913 12/1949 Amberg 2601023,311,151 3/1967 Willis et al. 26080.7 3,402,140 9/ 1968 Bickel et al26024 OTHER REFERENCES Rubber Age, vol. 70, No. 6, 1952. (pp. 735 to 747relied on).

Chatfield, H. W., Varnish Constituents, 1953, TP 938 C53 (pp. 196 to 199relied on).

DONALD E. CZAJA, Primary Examiner W. E. PARKER, Assistant Examiner US.Cl. X.R.

